CN102775548B - Method for polymerizing and preparing nanometer silver-PAAEM (Ploy Acetoacetoxyethyl Methacrylate) composite material through ultrasonically initiating emulsifier-free emulsion - Google Patents
Method for polymerizing and preparing nanometer silver-PAAEM (Ploy Acetoacetoxyethyl Methacrylate) composite material through ultrasonically initiating emulsifier-free emulsion Download PDFInfo
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- CN102775548B CN102775548B CN201210266847.5A CN201210266847A CN102775548B CN 102775548 B CN102775548 B CN 102775548B CN 201210266847 A CN201210266847 A CN 201210266847A CN 102775548 B CN102775548 B CN 102775548B
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Abstract
The invention relates to the field of nanometer silver-polymer composite materials, in particular to a method for polymerizing and preparing a nanometer silver-PAAEM (Ploy Acetoacetoxyethyl Methacrylate) composite material through ultrasonically initiating emulsifier-free emulsion. The method comprises the following steps of: dissolving silver nitrate into a proper amount of distilled water, agitating till the dissolution is complete, adding AAEM (Acetoacetyloxyethyl Methacrylate) and ammonium persulfate, putting into an ultrasonic reactor for reaction, gradually changing emulsion in a reaction system from milk white to grey, and refrigerating, demulsifying, upper liquid-removing, washing and drying the reacted emulsion to obtain the nanometer silver-PAAEM composite material. The method has the beneficial effects that under the conditions that the atmosphere protection is not used, and no reducing agent and no emulsifier are added, AAEM and AgNO3 solution is ultrasonically radiated, a silver ion is reduced into a nanometer silver particle, and in-situ polymerization is carried out on the AAEM at the same time to synthesize the nanometer silver-PAAEM composite material; and under the existence of the nanometer silver particle, the thermal property of the substrate PAAEM is greatly improved, and the active effects are generated.
Description
Technical field
The present invention relates to nanometer silver-polymer composites field, particularly a kind of ultrasonic initiation emulsifier-free emulsion polymerization is prepared the method for nanometer silver-PAAEM matrix material.
Background technology
At present, for the synthetic method of nanometer silver-polymer composites, mainly contain: ultraviolet radiation process, hole method, chemical reduction method and ultrasonic radiation method etc.Traditional method is that the polymerization of monomer is separated and carried out with the formation of nano silver particles, is then mixed to form matrix material by mechanicals efforts.But this method is difficult to nano silver particles to be evenly dispersed in polymeric matrix.
In order to overcome this drawback, Recent study person have transferred to sight line on two original position one-step synthesis nanometer silver-polymer composites.This method is that the reduction of silver ions and being aggregated in system of monomer are occurred simultaneously, and on the one hand, silver ions mixes with molecular form mutually with monomer, makes nanometer silver dispersed in matrix, is conducive to the performance study such as mechanics and optics of matrix material; On the other hand, nanometer silver can be distributed in polymeric matrix with progenitor, and polymkeric substance has stoped nanometer silver further to be reunited, thereby makes the peculiar property of nanometer silver obtain best embodiment and maintenance.
Simultaneously, it is synthetic that investigators find that radiation method can be good at realizing two original positions of nanometer silver-polymer composites, for example, two original position synthesizing nano-silver-PAN matrix materials under ultraviolet light irradiation, two original position synthesis of nano Ag-P4VP matrix materials under γ irradiation, two original position synthesizing nano-silver-PAMPS matrix materials under microwave radiation.
AAEM (AAEM); it is a kind of special polymer precursor; it is that a kind of very strong sequestrant contains again highly active methacrylate based group; and its homopolymer (PAAEM) has again good thermostability, can effectively protect stabilization inorganic nano-particle as matrix with PAAEM.Retrieval is found, exist AAEM and styrol copolymer successfully to prepare the ZrO2-PAAEM/PS nanoparticle with nucleocapsid structure as stablizer, but PAAEM stabilization nano metal particles be there is not yet bibliographical information.
In addition, ultrasonic have a trigger monomer polymerization at low temperatures, impels the reduction of silver ions, can make the advantages such as system is even by rapid stirring, be widely used in the preparation of nanometer silver-polymer composites, for example, synthesized nanometer silver-polymer composites etc. by ultrasonic radiation.But, exist more or less technical defect in synthetic, as used protective atmosphere, emulsifying agent, the unfavorable factor such as tensio-active agent etc. cause route of synthesis loaded down with trivial details, aftertreatment difficulty.
Summary of the invention
In order to solve the technical problem existing in prior art, the object of the present invention is to provide under a kind of condition that does not use atmosphere protection and emulsifying agent, adopt ultrasonic initiation emulsifier-free emulsion polymerization to prepare the method for nanometer silver-PAAEM matrix material.
The technical solution used in the present invention is as follows:
Ultrasonic initiation emulsifier-free emulsion polymerization is prepared the method for nanometer silver-PAAEM matrix material, it is characterized in that, Silver Nitrate is dissolved in appropriate distilled water, is stirred to completely and dissolves, then add AAEM and ammonium persulphate, being placed in ultrasonic reactor reacts, emulsion in reaction system is by oyster white grizzle gradually, and reacted emulsion, through refrigeration, breakdown of emulsion, discards supernatant liquid, washing, dry, obtains nanometer silver-PAAEM mixture.
Preferably, the mass ratio of Silver Nitrate, distilled water, AAEM and ammonium persulphate is: 6～7: 380～420: 8～12: 0.05～0.15.
More preferably, the mass ratio of Silver Nitrate, distilled water, AAEM and ammonium persulphate is: 6.5～6.7: 395～405: 9～11: 0.09～0.12.
Most preferably, the mass ratio of Silver Nitrate, distilled water, AAEM and ammonium persulphate is: 6.6: 400: 10: 0.1.
The present invention is not using atmosphere protection, is not adding under the condition of reductive agent and emulsifying agent, adopts ultrasonic radiation AAEM and AgNO
3solution, silver ions is reduced into nano-Ag particles, AAEM in-situ polymerization simultaneously, synthesizing nano-silver-PAAEM matrix material.The existence of nano silver particles makes matrix PAAEM thermal property improve a lot and produce active influence.
Accompanying drawing explanation
For the ease of it will be appreciated by those skilled in the art that the present invention is further illustrated below in conjunction with accompanying drawing.
Fig. 1 is the transmission electron microscope photo of nanometer silver-PAAEM matrix material.
Fig. 2 is (a) PAAEM and (b) the TG curve of nanometer silver-PAAEM matrix material.
Embodiment
Embodiment 1
The preparation of nanometer silver-PAAEM matrix material
0.66g Silver Nitrate is dissolved in 40g distilled water, be stirred to completely and dissolve, then add 1gAAEM and 0.01g ammonium persulphate, be placed in the ultrasonic 50min of ultrasonic reactor, emulsion in reaction system is by oyster white grizzle gradually, reacted emulsion, through refrigeration, breakdown of emulsion, discards supernatant liquid, washes the colloid three times of gained with water, to remove inorganic salt, use methanol wash three times, sample, through vacuum-drying, makes again.
Embodiment 2
The preparation of nanometer silver-PAAEM matrix material
0.6g Silver Nitrate is dissolved in 42g distilled water, be stirred to completely and dissolve, then add 0.9gAAEM and 0.012g ammonium persulphate, be placed in the ultrasonic 45min of ultrasonic reactor, emulsion in reaction system is by oyster white grizzle gradually, reacted emulsion, through refrigeration, breakdown of emulsion, discards supernatant liquid, washes the colloid three times of gained with water, to remove inorganic salt, use methanol wash three times, sample, through vacuum-drying, makes again.
Embodiment 3
The preparation of nanometer silver-PAAEM matrix material
0.67g Silver Nitrate is dissolved in 40.5g distilled water, be stirred to completely and dissolve, then add 1.2gAAEM and 0.005g ammonium persulphate, be placed in the ultrasonic 55min of ultrasonic reactor, emulsion in reaction system is by oyster white grizzle gradually, reacted emulsion, through refrigeration, breakdown of emulsion, discards supernatant liquid, washes the colloid three times of gained with water, to remove inorganic salt, use methanol wash three times, sample, through vacuum-drying, makes again.
Embodiment 4
The preparation of nanometer silver-PAAEM matrix material
0.65g Silver Nitrate is dissolved in 39.5g distilled water, be stirred to completely and dissolve, then add 0.8gAAEM and 0.015g ammonium persulphate, be placed in the ultrasonic 50min of ultrasonic reactor, emulsion in reaction system is by oyster white grizzle gradually, reacted emulsion, through refrigeration, breakdown of emulsion, discards supernatant liquid, washes the colloid three times of gained with water, to remove inorganic salt, use methanol wash three times, sample, through vacuum-drying, makes again.
Embodiment 5
The preparation of nanometer silver-PAAEM matrix material
0.7g Silver Nitrate is dissolved in 38g distilled water, be stirred to completely and dissolve, then add 1.1gAAEM and 0.009g ammonium persulphate, be placed in the ultrasonic 50min of ultrasonic reactor, emulsion in reaction system is by oyster white grizzle gradually, reacted emulsion, through refrigeration, breakdown of emulsion, discards supernatant liquid, washes the colloid three times of gained with water, to remove inorganic salt, use methanol wash three times, sample, through vacuum-drying, makes again.
Comparative example 1
The preparation of PAAEM matrix material
1gAAEM and 0.01g ammonium persulphate are added in reaction vessel, be placed in the ultrasonic 50min of ultrasonic reactor, emulsion in reaction system is by oyster white grizzle gradually, reacted emulsion, through refrigeration, breakdown of emulsion, discards supernatant liquid, washes the colloid three times of gained with water, to remove inorganic salt, use methanol wash three times, sample, through vacuum-drying, makes again.
Nanometer silver-PAAEM composite sample prepared by embodiment 1 is dispersed in acetone soln, get one drip paving be dispersed in 4.8 × 10
-2on the copper mesh of mm specification, after it is dry, carry out TEM test, acceleration voltage is 200kV, and the resolving power of instrument is 0.19nm.
Refer to Fig. 1, the nanometer silver particle diameter of ultrasonic preparation, at 10～30nm, is spherical or subsphaeroidal pattern.Illustrate that the in-situ polymerization of monomer and the in-situ reducing of silver ions are uniformly dispersed to preparation, the nano silver particles of narrow diameter distribution is highly beneficial.From electron diffraction photo, according to electron diffraction fundamental formular d=K/R and Electronic Speculum constant K (20.08mm.nm
-1), calculate the size of corresponding spacing d, be respectively 0.2362nm, 0.2049nm, 0.1445nm and 0.1232nm, basically identical with [111], [200], [220] and [311] spacing d value of PDF card #87-0597, illustrate that the nanometer silver making is centroid cubic crystal system polycrystalline structure.
Analyze combined instrument by heat solid powder sample (embodiment 1 and comparative example 1) is tested, high-purity N 2 constant flow rate are 80ml/min, and temperature rise rate is 10K/min.
Refer to Fig. 2, the decomposition temperature of nanometer silver-PAAEM matrix material is apparently higher than pure PAAEM, rate of decomposition is significantly lower than pure PAAEM, and this is consistent with the thermostability that the existence of the nano silver particles of the reports such as Heon-Su Park can improve composite polymer matrix.Its reason may be that nano silver particles is evenly dispersed in matrix PAAEM, produce interaction force with matrix, the existence of nano-Ag particles has suppressed the molecular chain movement of polymkeric substance, thereby has improved molecular chain at the required energy of heat-processed Fracture, and the decomposition temperature of polymkeric substance is improved.
In sum, the existence of nano-Ag particles produces actively impact to the thermal property of matrix PAAEM.
Above content is only that the present invention is conceived to example and explanation; affiliated those skilled in the art make various modifications to described specific embodiment or supplement or adopt similar mode to substitute; only otherwise depart from the design of invention or surmount this scope as defined in the claims, all should belong to protection scope of the present invention.
Claims (5)
1. ultrasonic initiation emulsifier-free emulsion polymerization is prepared the method for nanometer silver-PAAEM matrix material, it is characterized in that, Silver Nitrate is dissolved in appropriate distilled water, be stirred to completely and dissolve, add again AAEM and ammonium persulphate, being placed in ultrasonic reactor reacts, Silver Nitrate, distilled water, the mass ratio of AAEM and ammonium persulphate is: 6～7:380～420:8～12:0.05～0.15, the ultrasonic reaction time is 45～55min, emulsion in reaction system is by oyster white grizzle gradually, reacted emulsion is through refrigeration, breakdown of emulsion, discard supernatant liquid, washing, dry, obtain nanometer silver-PAAEM mixture.
2. ultrasonic initiation emulsifier-free emulsion polymerization according to claim 1 is prepared the method for nanometer silver-PAAEM matrix material, it is characterized in that, the mass ratio of Silver Nitrate, distilled water, AAEM and ammonium persulphate is: 6.5～6.7:395～405:9～11:0.09～0.12.
3. ultrasonic initiation emulsifier-free emulsion polymerization according to claim 2 is prepared the method for nanometer silver-PAAEM matrix material, it is characterized in that, the mass ratio of Silver Nitrate, distilled water, AAEM and ammonium persulphate is: 6.6:400:10:0.1.
4. the method for preparing nanometer silver-PAAEM matrix material according to the ultrasonic initiation emulsifier-free emulsion polymerization described in claim 1-3 any one, is characterized in that, described washing comprises water washing and methanol wash, washs respectively 3 times.
5. the method for preparing nanometer silver-PAAEM matrix material according to the ultrasonic initiation emulsifier-free emulsion polymerization described in claim 1-3 any one, is characterized in that, described dry employing vacuum-drying.
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